Polyoxometalate decorated Pt1-O pair for production of high-value-added fuels additive from alkylation reaction of unsaturated organic and aromatic hydrocarbons

The alkylation of unsaturated organic and aromatic hydrocarbons represents a pivotal class of synthetic reactions with significant implications in both industrial and academic research. Furthermore, cyclohexylbenzene, synthesized via the alkylation of benzene with cyclohexene, represents a high-value-added fuel additive owing to its exceptionally high cetane number. However, it still remains challenging due to the insufficient activation of double bond-containing organic substrate over traditional phosphotungstate catalysts. In this study, we develop a single Pt atom doped phosphotungstate, as Pt 1 -NH 4 -PW catalyst, through a coprecipitation method, for the alkylation of cyclohexene with benzene. Compared to pristine NH 4 -PW, Pt 1 -NH 4 -PW catalyst consists of the electronic reconstructed Pt 1 -O pair coordinated with [PW 12 O 40 ] 3− . Such structure shows a typical synergistic interaction characteristic, where the Pt atom of the Pt 1 -O structure serves as a Lewis acid site to accept the electron from the C=C bond, and the nearby O functions as hydrogen acceptors to promote C–H bond activation of benzene. Consequently, the Pt 1 -NH 4 -PW catalyst demonstrates a threefold enhancement in catalytic activity compared to NH 4 -PW for the alkylation of cyclohexene with benzene. The catalytic system further demonstrated exceptional performance in diverse transformations, including alkylation of benzene with either 1-hexene or 1-dodecene, and conversion of biomass-derived methyl oleate into high-value chemicals through alkylation.